CN105142787B - Process for preparing a sulphided catalyst - Google Patents
Process for preparing a sulphided catalyst Download PDFInfo
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- CN105142787B CN105142787B CN201480022860.3A CN201480022860A CN105142787B CN 105142787 B CN105142787 B CN 105142787B CN 201480022860 A CN201480022860 A CN 201480022860A CN 105142787 B CN105142787 B CN 105142787B
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- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 51
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 24
- -1 ether compound Chemical class 0.000 claims abstract description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 55
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 25
- 229910052717 sulfur Inorganic materials 0.000 claims description 23
- 239000011593 sulfur Substances 0.000 claims description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- 238000005987 sulfurization reaction Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- 229930195733 hydrocarbon Natural products 0.000 claims description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims description 15
- 150000002739 metals Chemical class 0.000 claims description 8
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 claims description 4
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 claims description 2
- 229920000180 alkyd Polymers 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 22
- 239000002994 raw material Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000003921 oil Substances 0.000 description 14
- 238000007493 shaping process Methods 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- 238000007598 dipping method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000005864 Sulphur Substances 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000008187 granular material Substances 0.000 description 7
- 239000011800 void material Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 150000002898 organic sulfur compounds Chemical class 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- PHTHEUNUXVDUOD-UHFFFAOYSA-N aluminum oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[O-2].[Al+3] PHTHEUNUXVDUOD-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a process for preparing a sulphided catalyst comprising the steps of (a) treating a catalyst carrier with one or more Group VIB metal components, one or more Group VIII metal components and a glycolic acid ethoxylate ether compound according to the formula (I) R-(CH2)x-CH2-O-[-(CH2)2-O-]m-CH2-COOH (I) wherein R is a hydrocarbyl group containing of from 5 to 20 carbon atoms,x is in the range of from 1 to 15, and m is in the range of from 1 to 10, and wherein the molar ratio of compound (I) to the Group VIB and Group VIII metal content is at least 0.01:1to 1:0.01;(b)drying the treated catalyst carrier at a temperature of at most 200 DEG C to form a dried impregnated carrier; and (c) sulphiding the dried impregnated carrier to obtain a sulphided catalyst.
Description
Technical field
The present invention relates to a kind of method of the catalyst for preparing sulfuration.
Background technology
In oil refining process, charging such as crude oil, distillation and irreducible oil fraction usually contains pollutant, these pollutant
Often it is used in the catalyst inactivation of chemical conversion charging.Especially abundant pollutant are sulfur-containing compound, such as hydrogen sulfide and are contained
Sulfur hydro carbons, and nitrogen-containing compound.
Hydroprocessing technique is used to this pollutant be removed from refinery stock and is usually directed to make hydrocarbon charging in hydrogen
In the presence of contact with hydrotreating catalyst under hydroprocessing conditions.Depollution thing removes outer, it is also possible to occur further
Conversion be such as hydrocracked and aromatic hydrogenation.
Hydrotreating catalyst includes hydrogenation metal component on oxide carrier.Hydrogenation metal component is usually group vi
Metal component such as molybdenum and/or tungsten and group VIII metal component such as nickel and/or cobalt.Hydrogenation metal component often vulcanizes as metal
Thing is present.Metal component can be incorporated in carrier in the form of sulfide, but generally before the procedure or is starting what is operated
During be converted into sulfide by making catalyst vulcanization.Hydrotreating catalyst was set to vulcanize quilt before operation is used it for
Referred to as presulfurization is processed.Sulfur-containing compound in processing for presulfurization includes mercaptan, sulfide, disulphide, polysulfide
And sulfoxide.
Presulfurization processes the hydrotreating catalyst for producing the hydroprocessing activity for showing raising.In view of needing what is met
Increasingly stricter environmental requirement, showing the active hydrotreating catalyst of improvement is just becoming more and more important.
In addition to the use that presulfurization is processed, also it is currently in use organic compound further to improve hydrotreating catalyst
Activity.
In this regard, can be mentioned that such as EP-A-0496592.In the patent specification, it is proposed that a kind of to prepare sulfuration
The method of hydrotreating catalyst, wherein by the metal of periodic table of elements group vi and group VIII, carboxylic acid such as glycolic, Fructus Citri Limoniae
Acid or gluconic acid and organosulfur compound mix with carrier material, thereafter that the mixture kneading, molding is simultaneously and then dry
It is dry.
Additionally, in US-A-2012/0168350, describing a kind of preparation for the slurry catalytic of heavy oil feed of upgrading
The method of agent compositionss.Methods described includes that offer is included in vib metals precursor and group VIII metal precursor at least
One of inorganic metallic precursor solution；Mixing polar non-solute is dispersibled with the inorganic metallic precursor solution with forming oil
Inorganic metallic precursor, and provide vulcanizing agent so that the oily dispersible inorganic metallic precursor vulcanizes to form slurry catalyst.
The polar non-solute is the solvent of such as N-Methyl pyrrolidone (NMP) and dimethylformamide (DMF).
US-A-2012/0145600 describes a kind of method for preparing the solution for catalyst preparation, and the solution leads to
Cross i) at least one phosphorus compound, ii in an aqueous medium) at least one group vi metallic compound, iii) at least one the
Group VIII metal compound and iv) one or more specific ethylene glycol is merged together to be formed.Optionally include organic acid.
It is an object of the invention to provide a kind of method of the catalyst for preparing sulfuration, the catalyst of the sulfuration shows
The hydroprocessing activity of improvement.
The content of the invention
Having now found that in the ether carboxylic acid using particular category can accomplish this point.
Therefore, the invention provides a kind of method of the catalyst for preparing sulfuration, the method comprising the steps of：
A () is with one or more vib metals component, one or more group VIII metal component and according to formula (I)
Glycolic acid ethoxylate thing ether compound process catalyst carrier
R-(CH2)x-CH2-O-[-(CH2)2-O-]m-CH2-COOH (I)
Wherein R is the alkyl containing 5 to 20 carbon atoms, and x is in the range of 1 to 10, and m is in the range of 1 to 10, and
And wherein compound (I) is 0.01 relative to the mol ratio of group vib and group VIII tenor described in the:1 to 1:0.01；
B () is dried the catalyst carrier of Jing process to form the impregnated carrier of drying at a temperature of at most 200 DEG C；With
C () makes the impregnated carrier of drying vulcanize to obtain the catalyst of sulfuration.
According to the present invention, there is provided a kind of method of the catalyst for preparing sulfuration, compared with known method, the catalysis
Agent is prepared in environmentally more attracting mode, while showing the hydroprocessing activity of improvement.
Specific embodiment
It can be suitably the carrier of metal component and with fair to stay in the catalyst carrier processed in step (a)
Perhaps any material of the porosity that the carrier is filled with formula (I) compound.Porous refractory oxide is usually used as carrier material
Material.The suitable example of possible suitable porous refractory oxide includes silicon oxide, aluminium oxide, titanium oxide, zirconium oxide, oxidation
Silicon-aluminium oxide, silica-titania, silica-zirconia, titanium dioxide-aluminum oxide, Zirconia-alumina, silicon oxide-oxidation
Titanium and in them both or more persons combination.Preferred porous refractory oxide in for the preparation of compositionss is suitable
The one kind of ground selected from aluminium oxide, silicon oxide and silica-alumina.Wherein, most preferred porous refractory oxide is aluminium oxide,
More particularly gamma-alumina.
According to measured by ASTM tests D-4222, porous refractory oxide could generally haveIn the range of
Average pore diameter.The total pore space volume of porous refractory oxide is preferably in the range of 0.2-2cc/ gram.
As measured by B.E.T. methods, the surface area of porous refractory oxide is usually more than 100m2/ gram, and generally exist
100-400m2/ gram in the range of.The surface area tests D3663-03 measurements by BET method according to ASTM.
Carrier to be used can be in the form of shaped granule.Shaping carrier can pass through well known by persons skilled in the art any
It is prepared by appropriate method.
Generally, form of the porous refractory oxide parent material in powder and with water and (if necessary to or it is necessary) other are changed
Auxiliary agent such as peptizer, flocculant, binding agent or other compound mixing are learned to form mixture or paste, the mixture or paste
Agent is formed as aggregate or shaped granule.It may be desirable that extrude the mixture with formed it is variously-shaped in any one
Plant or various extrudates, such as nominal size is such as 1/16 inch, 1/8 inch and 3/16 inch of cylindrical shape and trilobal.
Then the aggregate comprising one or more inorganic oxide compound listed earlier or shaped granule are dried and are calcined with
Provide final molding carrier granular used according to the invention.
Before being used in the present invention, the shaping carrier particle, standard drying conditions can be dried under standard drying conditions
May include the baking temperature in the range of 50 to 200 DEG C, preferably 75 to 175 DEG C and more preferably 90 to 150 DEG C.
After drying, generally calcine the shaping carrier particle under standard calcination condition, standard calcination condition include 250 to
900 DEG C, preferably 300 to 800 DEG C and most preferably 350 to 600 DEG C of calcining heat.
The surface area of the shaping carrier calcined and void content allow the change of shaping carrier metal component and formula (I)
Compound impregnates.The shaping carrier of Jing calcinings can have in 50-450m2/ g, preferably 75-400m2/ g and most preferably 100-
350m2Surface area in the range of/g.
Jing calcine shaping carrier with angstromFor unit average pore diameter preferably 50-200, preferably 70-150,
And most preferably in the range of 75-125.
The void content of Jing calcining shaping carriers is preferably greater than 0.5cc/g and generally in the range of 0.5-1.1cc/g.More
Normally, in the range of 0.6-1.0cc/g, most generally, it is 0.7-0.9cc/g to void content.Preferably, Jing is sintered into
The total pore space volume less than 10% of type granule is contained in pore diameter and is more thanHole in, it is highly preferred that Jing is sintered into
The total pore space volume less than 7.5% of type granule is contained in pore diameter and is more thanHole in, and most preferably, be less than
5%.
The pore size distribution and void content of Jing calcinings shaped granule mentioned in this article is referred to as by mercury injection apparatus
Those properties that method (ASTM Test Method D 4284) is measured.The measurement of the pore size distribution of Jing calcining shaped granules is by appointing
The hydrargyrum surface tension of what suitable measuring instrument, the contact angle using 140 ° and 474 dynes/cm is carried out at 25 DEG C.
Shaping carrier, it has preferably been calcined, and one or more vib metals group can be contained used in one-dip
Point, the single solution impregnation of one or more group VIII metal component and formula (I) compound.
The metallic element of metal component is selected from such as《Chemistry and physics handbook》(the 63rd edition) (Handbook of
Chemistry and Physics 63rdEdition the periodic table of elements vib (preferably, chromium, molybdenum and tungsten) described in)
With group VIII (preferably, cobalt and nickel) those.Phosphorus is also likely to be desired component.
Metal component can be metal itself or any component containing the metal, including but not limited to metal-oxide, metal
Hydroxide, metal carbonate and slaine.
For group VIII metal, metal component be preferably selected from group VIII metal acetate, formates, citrate,
Oxide, hydroxide, carbonate, sulfate and both or more persons.Preferably, group VIII metal component be nickel and/
Or the metal-oxide of cobalt, hydroxide and/or carbonate.
For vib metals component, preferred component is selected from vib metals oxide and sulfide.
Preferably, carrier is first with one or more vib metals component and one or more group VIII metal group
Office is managed, and subsequently with the compound treatment according to formula (I).Most preferably, carrier is with both comprising one or more vib gold
Single solution of the category component again comprising one or more group VIII metal component is processed, and is dried, and subsequently with according to formula (I)
Compound treatment.
Preferably select the concentration of metallic compound in dipping solution so that needed for providing in the final present composition
Tenor, wherein by the aqueous solution void content and formula (I) chemical combination to be introduced in carrier material therein to be impregnated
The amount of thing is taken into account.This technology is also referred to as void content dipping.Generally, the concentration of metal component exists in dipping solution
0.01-100 mole per liter in the range of.
Formula (I) compound phase preferably exists for the ratio of metal (that is, the total amount of above-mentioned vib and group VIII metal)
0.4:1 to 3:1 (w/w), more preferably 0.5:1 to 2:In the range of 1.Additionally, formula (I) compound phase is soaked for metal
The ratio of stain carrier (that is, the total amount of vib and group VIII metal and carrier) is preferably 0.05:1 to 1:1 (weight/weight
Amount), more preferably 0.1:1 to 0.6:In the range of 1.Most preferably, weight of the weight amount of formula (I) compound in active metal
In the range of amount.
Dipping solution comprising metal component and/or formula (I) compound can also comprising suitably offer formula (I) compound
And/or the solvent of the dissolving of metallic compound.Possible solvent includes water and alcohol, such as methanol and ethanol.For formula (I) compound
For, water is preferred solvent.
Any suitable device or method can be adopted in the dipping of shaping carrier formula (I) compound and metal component,
Condition is devices which or method provides formula (I) compound and metal component to the intrapore suitable introducing of carrier material or
Dipping.Applying the example of the appropriate method of solution to shaping carrier may include to soak or sprays.
So that the method for optimizing that carrier is contacted with dipping solution is any suitable dipping well known by persons skilled in the art
Method, for example, by just wet dipping, thus, the amount or volume for being added to the solution of shaping carrier causes the total of added solution
Volume be can the up to about stand-by solution impregnation shaping carrier obtained void content amount.
The tenor of the shaping carrier of introducing metal component may depend on catalyst and treat wherein together with formula (I) compound
Application, but typically for hydrotreating application, more particularly group VIII metal component, cobalt and/or nickel, preferably nickel
The overall dry weight of catalyst of sulfuration can be based on in 0.5-20 weight %, preferably 1-15 weight % and most preferably 2-12
Amount in the range of weight % is present in the catalyst of sulfuration.
Vib metals component, more particularly molybdenum and/or tungsten, preferably molybdenum can be based on the gross dry weight of the catalyst of sulfuration
Meter, with 5-50 weight %, preferably 8-40 weight % and the most preferably amount introducing molding in the range of 12-30 weight %
In carrier.
The dry weight of the catalyst of sulfuration is based on above for the percetage by weight that metal component is referred to, while metal component quilt
It is assumed that exist as element, but regardless of the actual form of metal component, such as oxide form or sulphided form.
Suitably have 250 to the 1500, number preferably in the range of 300 to 1000 equal according to the compound of formula (I)
Molecular weight.
In formula (I), R is the alkyl containing 5 to 20 carbon atoms.Alkyl is to remove the hydrocarbon of hydrogen from it.R is only by hydrogen and carbon
Composition.R can contain one or more unsaturated bonds, including aromatic hydrocarbons key.Preferably, R is the alkyl containing 6 to 15 carbon atoms, more excellent
Selection of land has the alkyl of 6 to 12 carbon atoms.
In formula (I), x is in the range of 1 to 10.For some compounds, R and x are not yet fixed.One example is for wherein
Ingredient R- (CH2)x- for alkyl chain situation.Under those circumstances, R and x are defined so that R and (CH2)xIn carbon it is former
Subnumber it is identical or as close possible to component.In the later case, R is chosen to have the compound of larger carbon number.
In formula (I), x in the range of 1 to 15, preferably in the range of 2 to 12, more preferably 3 to 10 model
In enclosing.
Number m in the range of 1 to 10, more preferably in the range of 1 to 5.Most preferably, m is 1 to 3.
Preferably, glycolic acid ethoxylate thing oleyl ether, glycolic acid ethoxylate thing nonyl are selected from according to the compound of formula (I)
Base phenyl ether and glycolic acid ethoxylate thing lauryl ether.It is highly preferred that being glycolic acid ethoxylate according to the compound of formula (I)
Thing oleyl ether.
In step (b), the catalyst carrier of Jing process is dried at a temperature of at most 200 DEG C to form the leaching of drying
Stain catalyst.
It is important that the baking temperature in step (b) is not too high.According to the present invention, baking temperature is at most 200 DEG C.It is excellent
Selection of land, impregnated carrier is less than 180 DEG C in its lower dry baking temperature, and most preferably, the baking temperature is less than 175
℃.It should be understood that this drying steps generally will be carried out under than above-mentioned temperature lower temperature, and generally, being dried will
Carry out at a temperature of in the range of 60-150 DEG C.
It is preferred that so that providing the side that gained drying impregnated carrier has the volatile content less than 20 weight %LOI
Formula controls the drying of impregnated carrier.It is preferred that the LOI of drying impregnated carrier is in 1-20 weight %LOI and most preferably 3-15 is heavy
In the range of amount %LOI.
LOI, or loss on ignition, are defined as in the air that it is exposed at a temperature of 482 DEG C material after the time period of two hours
Percent weight loss.LOI can be expressed from the next：(example weight before exposure deducts the example weight after exposure) takes advantage of
100 again divided by (example weight before exposure).
In the drying of impregnated carrier, expect to remove compound (I) as few as possible.It is preferably based on and is incorporated into dipping
The gross weight meter of the compound (I) in carrier remains in the drying of gained more than the introduced compound (I) of 50 weight %
In impregnated carrier.Preferably, the amount of the compound (I) being retained in drying impregnated carrier more than 75 weight %, and most preferably
Ground, is initially added in the compound of drying impregnated carrier (I) and is retained in the impregnated carrier of drying more than 90 weight %.
Therefore, during drying steps, should be from dipping less than the compound (I) for being initially added to drying impregnated carrier of 50 weight %
Carrier is removed.Preferably, during drying steps (b), less than 25 weight %, most preferably less than 10 weight % Jing is incorporated into
The compound (I) being dried in impregnated carrier is removed.
Based on overall dry weight, the drying impregnated carrier obtained in preferred steps (b) contains the sodium of at most 0.5 weight %,
More particularly at most 0.1 weight %, most particularly at most 0.05 weight %.
The impregnated carrier of the present invention can be with sulphur compound ex situ or in-situ treatment.Impregnated carrier can In-situ sulphiding exactly sheet
One of favorable characteristics of invention, it allows to transport unvulcanized compositionss and is delivered to reactor, wherein, the compositionss
Hydrogen process step can be optionally present by vulcanisation step in-situ activation before the vulcanisation step.In the activation of impregnated carrier
In, preferably processed with sulphur compound, hydrogen process is optionally present before the process.
Optional hydrogen processes and may include to make impregnated carrier be exposed to hydrogeneous gas atmosphere at a temperature of up to 250 DEG C.
Preferably, hydrogen under the hydrogen treatment temperature in the range of 100-225 DEG C and most preferably in the range of 125-200 DEG C processes temperature
Impregnated carrier is set to be exposed to hydrogen under degree.
The hydrogen dividing potential drop of the gas atmosphere used in hydrogen process step generally can be in 1-70 bars, preferably 1.5-55 bars and most
Preferably in the range of 2-35 bars.Make to contact 0.1- under the conditions of the temperature and pressure that impregnated carrier is previously mentioned with gas atmosphere
Hydrogen process time section in the range of 100 hours, and preferably, hydrogen process time section is 1-50 hours, and most preferably 2-30
Hour.
The sulfuration of impregnated carrier can be carried out using any conventional method well known by persons skilled in the art.Therefore, leaching can be made
Stain carrier is contacted with sulfur-containing compound under the contact conditions of the present invention, and the sulfur-containing compound can be hydrogen sulfide or be decomposed into
The compound of hydrogen sulfide.The example of such decomposable compound includes mercaptan, CS2, thiophene, dimethyl sulfide (DMS) and two
Methyl disulfide (DMDS).Furthermore it is preferred that sulfuration is certain by making compositionss under the conditions of suitable vulcanizing treatment and containing
The hydrocarbon feed of the sulfur-containing compound of concentration contacts to realize.The sulfur-containing compound of hydrocarbon feed can be organosulfur compound, particularly
By usual those contained in the petroleum distillate that hydrodesulfurizationprocess process is processed.
Suitable vulcanizing treatment condition is that of conversion from the active metal component of impregnated carrier to its sulfur form that provide
A bit.Generally, impregnated carrier its lower contact sulfur-containing compound curing temperature at 150-450 DEG C, preferably 175-425 DEG C and
Most preferably in the range of 200-400 DEG C.
When using it is stand-by the present invention carbon monoxide-olefin polymeric hydrotreating hydrocarbon feed when, conditions of vulcanization can be hydrogenated with
The process conditions of process are identical.Impregnated carrier its lower sulfuration sulfide stress generally can 1-70 bars, preferably 1.5-55 bars,
And most preferably in the range of 2-35 bars.
One of beneficial effect that the present invention is provided is that it can be used on and postpones to feed the anti-of introducing program starting with so-called
In answering device system.It is introduced in program charging is postponed, experiences first including the reactor assembly of the reaction vessel containing impregnated carrier
Heating stepses to lift the temperature of reactor and impregnated carrier contained therein, for the introducing of vulcanizing agent or heated hydrocarbon feed
It is ready to process.This heating steps may include to introduce hydrogen in reactor under the hydrogen treatment conditions being previously mentioned
Body.Impregnated carrier can be processed with sulfur-containing compound in mode such as previously described herein.
It should be understood that the impregnated carrier of the present invention is after it is with sulphuring treatment, it is the height in the hydrotreating for hydrocarbon feed
Spend effective catalyst.The catalyst is particularly useful in the application of the hydrodesulfurization of hydrocarbon feed or hydrodenitrogeneration is related to, and
Especially have found its be for distillate raw material (particularly diesel oil) prepare sulphur concentration less than 15ppmw, be preferably lower than
Excellent catalysts in the hydrodesulfurization of the super-low sulfur distillation product of 10ppmw and most preferably less than 8ppmw.
In hydrotreating application, impregnated carrier is set (to be optionally used in delay charging to be introduced in program or otherwise
With sulphuring treatment) contact with the hydrocarbon feed that generally there is certain density sulfur under suitable hydrodesulfurizationconditions conditions.It is more typical and excellent
The hydrocarbon feed of choosing is oil middle distillate fraction of the boiling temperature in the range of 140-410 DEG C at atmosheric pressure.These temperature
Spend the substantially initial and boiling temperature for middle distillate.It is intended to the example of refinery stream for including in the implication of middle distillate
It is included in the straight-run fuel of boiling in mentioned boiling range, such as kerosene, jet fuel, light diesel fuel, heating oil, weight
Matter diesel oil, and cracked distillate such as FCC recycle oils, coker gas oil and it is hydrocracked distillation.The distillation hydrogenation of the present invention
The preferred feedstock of sulfur removal technology is the middle distillate seethed with excitement in 140-400 DEG C of diesel boiling range.
The sulphur concentration of middle distillate raw material can be high concentration, such as weight based on elementary sulfur and including sulfur-containing compound
In the interior gross weight meter for distillating raw material in the range of up to 2 weight % for distillating raw material.But generally, present invention side
The sulphur concentration for distillating raw material of method is in the range of 0.01-1.8 weight % (100-18,000ppmw).But more generally, sulfur is dense
Spend the model in 0.1-1.6 weight % (1000-16,000ppmw), most commonly 0.18-1.1 weight % (1800-11,000ppmw)
In enclosing.It should be understood that the sulfur content for distillating raw material mentioned in this article refers to distillate in raw material or hydrodesulfurization is distillated
Those compounds of common and for sulfur atom-containing compound in produce product, and it generally includes organosulfur compound.
The catalyst of the sulfuration prepared by the present invention is in the application of the catalytic hydrogenation treatment of petroleum derived feed is related to
(in the hydrotreating of normal pressure distillation, gas oil and residue and vacuum gas oil and residue) is particularly useful.With it is known
Hydrotreating catalyst compare, the compositionss are it has been found that superior hydrodesulfurization activity and present good catalysis
Stability.
Therefore the present invention additionally provides a kind of method of hydrotreating sulfur-bearing hydrocarbon feed, and methods described includes making hydrocarbon feed exist
Contact with catalyst prepared in accordance with the present invention at a temperature of the hydrogen dividing potential drop of 1 to 70 bar and 200 to 420 DEG C.
The impregnated carrier of the present invention can be used as a part for any suitable reactor assembly, and the reactor assembly is provided
Impregnated carrier or derivatives thereof with distillate contact of the raw material under suitable hydrodesulfurizationconditions conditions, the hydrodesulfurizationconditions conditions can
Presence and elevated stagnation pressure and temperature including hydrogen.Such suitable response system may include fixed catalyst bed system, boiling
Catalyst bed system, slurried catalyst system and fluidized catalyst bed systems.Preferred reactor assembly is to urge comprising the present invention
Those of the fixed bed of agent, the fixed bed is included in reaction vessel, and the reaction vessel is equipped with reactor feed and enters
Mouth device (such as feed nozzle) distillates raw material and reactor effluent outlet device (such as effluent to introduce in reaction vessel
Outlet nozzle) taking hydrocarbon products or the super-low sulfur distillation product that reactor effluent or Jing are processed away from reaction vessel.
Hydrodesulfurization is generally in 689.5-13,789kPa (100-2000psig), preferably 1896-10,342kPa
(275-1500psig) the hydrodesulfurization reaction pressure and in the range of more preferably 2068.5-8619kPa (300-1250psig)
Lower operation.
Hydrodesulfurization reaction temperature is generally in 200-420 DEG C (392-788 ℉), preferably 260-400 DEG C (500-752
℉) and in the range of most preferably 320-380 DEG C (608-716 ℉).It should be understood that expecting using compositionss of the invention
Less than one of feature be that it has the significantly higher catalysis activity of the carbon monoxide-olefin polymeric substituted than some other and therefore
For the raw material hydrotreating of specified rate, its commonly provided relatively low required technological temperature.
The flow rate for distillating the reaction zone that raw material is added to the inventive method generally causes to provide in 0.01-10hr-1Scope
Interior liquid hourly space velocity (LHSV) (LHSV).As used herein, term " liquid hourly space velocity (LHSV) " refers to that distillating raw material is added to the anti-of the inventive method
The speed (volume is per hour) in area is answered divided by distillating the numeric ratio that raw material is added to the volume of catalyst contained in reaction zone.
Preferred LHSV is in 0.05-5hr-1, more preferably 0.1-3hr-1And most preferably 0.2-2hr-1In the range of.
It is preferred that being hydrogenated with to the reaction zone of the inventive method with distillation starting materials.In this case, hydrogen is sometimes referred to
For hydrogen processing gas.Hydrogen processing gas ratio is relative to the amount for distillating raw material for being added to reaction zone and usual upper for the amount of hydrogen
To 1781m3/m3(10,000SCF/bbl) in the range of.Preferred process gas ratio is in 89-1781m3/m3(500-10,
000SCF/bbl), more preferably 178-1602m3/m3(1,000-9,000SCF/bbl) and most preferably 356-1425m3/m3
(2,000-8,000SCF/bbl) in the range of.
Originate from the inventive method desulfurization distillation product have it is low or relative to distillate raw material reduction sulphur concentration.
One particularly advantageous aspect of the inventive method is that its diesel product that can provide deep desulfuration or ultra-low-sulphur diesel are produced
Product.As having been pointed out herein, low-sulfur distillation product can have the sulphur concentration less than 50ppmw or as described in elsewhere herein
Any other pointed sulphur concentration (for example, less than 15ppmw or less than 10ppmw or less than 8ppmw).
Following examples are presented further to illustrate certain aspects of the invention, but these embodiments to should not be construed as limiting
The scope of the present invention.
Embodiment
Embodiment 1-catalyst A (according to the present invention)
Phosphoric acid (the H of weight % of 4.64g 85 is diluted with demineralized water3PO4) to 16.5ml volume and to its addition
10.34g molybdenum oxide (MoO3) and 2.76g nickelous carbonates (Ni of 41 weight %).Then under agitation heating blends are clear to obtain
Clear solution, then allows the solution to be cooled to room temperature.This is hereafter referred to as stock solution.
Stock solution is divided into into quarter.Portion is further diluted with 3.5ml demineralized waters, and is soaked using resulting solution
Stain 9.0g at 300 DEG C predrying 1h gamma-alumina extrudate.Impregnated extrudate is dried at a temperature of 100 DEG C
4h.Finally, the drying of 5.0g parts is impregnated with 1.8g glycolic acid ethoxylates thing 4- nonylplenyl ethers (number-average molecular weight is 600)
Product, and no longer calcine.
Embodiment 2-catalyst B (comparative catalyst)
To in second part of stock solution of embodiment 1 add 0.5ml water, 1.04ml citric acid solutions (50 weight %) and
2.24ml mean molecule quantities are 200 Polyethylene Glycol (PEG-200) and stir 1 hour.Impregnated using gained settled solution
9.0g at 300 DEG C predrying 1h gamma-alumina extrudate.Product is dried 4h at a temperature of 100 DEG C, and no longer calcines.
Embodiment 3-catalyst C (comparative catalyst)
The present embodiment represents the teaching of US-A-2012/0145600.
By the phosphoric acid for adding a small amount of water followed by 0.295g 85% in 0.69g nickelous carbonates (Ni of 41 weight %)
Suspended substance is prepared with 1.03g molybdenum oxides.Suspended substance is heated at 92 DEG C until it becomes to stir.Then divide at 92 DEG C
Aliquot adds other 1.55g molybdenum oxides.At this temperature further stirring mixture is until obtain the solution of clarification, and make its cold
But to room temperature.0.7ml water, 1.04ml citric acid solutions (50 weight %), the phosphorus of 0.49ml 85% are sequentially added in the solution
Sour and last 2.24ml mean molecule quantities are 200 Polyethylene Glycol (PEG-200).Shaking mixture is simultaneously put in 60 DEG C of baking oven
Put 1 day.Mixture is allowed to be cooled to room temperature and shake again.The 9.0g predrys at 300 DEG C are impregnated using gained settled solution
The gamma-alumina extrudate of dry 1h.Product is dried 4h at a temperature of 100 DEG C, and no longer calcines.
4-hydrodesulfurization performance of embodiment
Catalyst A-C is respectively provided with identical content of metal：Based on dry weight meter, the Ni of 2.65 weight %, 13.5 weight %
Mo, the P of 2.45 weight %.
Tested in hydrotreating simulation test using the gas oil feedstocks with property shown in table 1.
Table 1
Tested in the one way microfluidic device for being mounted with the catalyst bed comprising 0.53ml catalyst, the catalyst
It is crushed and be screened to 30-80 mesh sieve fractions.
Before test, catalyst is adjusted in advance in hydrogen at 150 DEG C, and and then using the gas-oil feed for having mixed sulfur
With hydrogen under the pressure of 40 bars and using final temperature that 340 DEG C are risen to from 150 DEG C temperature curve carry out it is liquid phase presulphiding.
To measure hydrodesulfurization activity, make gas oil feedstocks and catalyst bed with one-pass operation in 1.15 liters of per liter of gas oils
Catalyst is per hour under the stagnation pressure of the air speed of (l/l/h), the hydrogen/heavy gas oil ratio of 350Nl/kg and 40 bars (4.0MPa)
Contact.
The residual sulfur of the product obtained under 355 DEG C of catalyst bed temperature and after putting into production 72 hours by measuring contains
Measure to assess hydrodesulfurization performance.The result illustrated in table 2 shows that catalyst according to the invention A is more aobvious than comparative catalyst B and C
Write more activity.
Table 2
| S(ppm) | |
| Catalyst A | 19 |
| Catalyst B | 37 |
| Catalyst C | 164 |
Claims (5)
1. the method for preparing the catalyst of sulfuration, the method comprising the steps of：
A () uses with one or more vib metals component and one or more group VIII metal component and subsequently second first
Alkyd ethoxylate ether compound processes catalyst carrier, and the glycolic acid ethoxylate thing ether compound is selected from glycolic second
Epoxide compound oleyl ether, glycolic acid ethoxylate thing nonylplenyl ether and glycolic acid ethoxylate thing lauryl ether, and wherein
The glycolic acid ethoxylate thing ether compound is at least relative to the mol ratio of the vib and group VIII tenor
0.01:1 to 1:0.01；
B () catalyst carrier that the drying Jing is processed at a temperature of at most 200 DEG C is forming the impregnated carrier of drying；With
C () makes the impregnated carrier of the drying vulcanize to obtain the catalyst of sulfuration.
2. method according to claim 1, wherein the glycolic acid ethoxylate thing ether compound has 250 to 1500
Molecular weight.
3. method according to claim 1 and 2, wherein the carrier is aluminium oxide.
4. method according to claim 3, wherein the carrier is gamma-alumina.
5. the method for hydrotreating sulfur-bearing hydrocarbon feed, methods described includes making the hydrocarbon feed in the hydrogen dividing potential drop and 200 of 1 to 70 bar
Contact with the catalyst prepared according to any one of Claims 1-4 at a temperature of 420 DEG C.
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| EP13164937.8 | 2013-04-23 | ||
| PCT/EP2014/058103 WO2014173878A1 (en) | 2013-04-23 | 2014-04-22 | Process for preparing a sulphided catalyst |
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| EP (1) | EP2988870B1 (en) |
| KR (1) | KR102216537B1 (en) |
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| CN104646010B (en) * | 2015-01-29 | 2017-09-05 | 中国海洋石油总公司 | A kind of process modification method of sulfurized hydrogenation catalyst for refining |
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| JPH04243547A (en) | 1991-01-22 | 1992-08-31 | Sumitomo Metal Mining Co Ltd | Manufacture of hydrogenation catalyst for hydrocarbon oil |
| JPH061722A (en) * | 1992-04-24 | 1994-01-11 | Nippon Suisan Kaisha Ltd | Carcinogenic promotion inhibitor |
| JP2900771B2 (en) * | 1992-11-18 | 1999-06-02 | 住友金属鉱山株式会社 | Method for producing catalyst for hydrotreating hydrocarbon oil |
| JP3802106B2 (en) * | 1995-06-08 | 2006-07-26 | 日本ケッチェン株式会社 | Hydrocarbon oil hydrotreating catalyst, production method thereof and activation method thereof |
| PL1680486T3 (en) * | 2003-10-03 | 2023-01-09 | Albemarle Netherlands B.V. | Process for activating a hydrotreating catalyst |
| AU2007207629B2 (en) * | 2006-01-17 | 2011-11-24 | Exxonmobil Research And Engineering Company | Selective catalysts for naphtha hydrodesulfurization |
| CA2771827C (en) * | 2009-08-24 | 2017-11-28 | Albemarle Europe Sprl | Solutions and catalysts comprising group vi metal, group viii metal, and phosphorus |
| US8778828B2 (en) | 2010-12-30 | 2014-07-15 | Chevron U.S.A. Inc. | Hydroprocessing catalysts and methods for making thereof |
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